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  Signatures of Solvation Thermodynamics in Spectra of Intermolecular Vibrations

Persson, R. A. X., Pattni, V., Singh, A., Kast, S. M., & Heyden, M. (2017). Signatures of Solvation Thermodynamics in Spectra of Intermolecular Vibrations. Journal of Chemical Theory and Computation, 13(9), 4467-4481. doi:10.1021/acs.jctc.7b00184.

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ct7b00184_si_001.pdf (Supplementary material), 7MB
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Persson, Rasmus A. X.1, Author              
Pattni, Viren1, Author              
Singh, Anurag1, 2, Author              
Kast, Stefan M.3, Author
Heyden, Matthias1, Author              
Affiliations:
1Research Group Heyden, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1950292              
2Department of Chemistry, Indian Institute of Technology, Roorkee, IN-247667 Roorkee, Uttarakhand, India, ou_persistent22              
3Physikalische Chemie III, Technische Universität Dortmund, Otto-Hahn-Straße 4a, DE-44227 Dortmund, Germany, ou_persistent22              

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 Abstract: This study explores the thermodynamic and vibrational properties of water in the three-dimensional environment of solvated ions and small molecules using molecular simulations. The spectrum of intermolecular vibrations in liquid solvents provides detailed information on the shape of the local potential energy surface, which in turn determines local thermodynamic properties such as the entropy. Here, we extract this information using a spatially resolved extension of the two-phase thermodynamics method to estimate hydration water entropies based on the local vibrational density of states (3D-2PT). Combined with an analysis of solute–water and water–water interaction energies, this allows us to resolve local contributions to the solvation enthalpy, entropy, and free energy. We use this approach to study effects of ions on their surrounding water hydrogen bond network, its spectrum of intermolecular vibrations, and resulting thermodynamic properties. In the three-dimensional environment of polar and nonpolar functional groups of molecular solutes, we identify distinct hydration water species and classify them by their characteristic vibrational density of states and molecular entropies. In each case, we are able to assign variations in local hydration water entropies to specific changes in the spectrum of intermolecular vibrations. This provides an important link for the thermodynamic interpretation of vibrational spectra that are accessible to far-infrared absorption and Raman spectroscopy experiments. Our analysis provides unique microscopic details regarding the hydration of hydrophobic and hydrophilic functional groups, which enable us to identify interactions and molecular degrees of freedom that determine relevant contributions to the solvation entropy and consequently the free energy.

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Language(s): eng - English
 Dates: 2017-02-202017-08-072017-09-12
 Publication Status: Published in print
 Pages: 5
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jctc.7b00184
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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 13 (9) Sequence Number: - Start / End Page: 4467 - 4481 Identifier: ISSN: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832